BN-Embedded Perylenes

Abstract

Transition metal catalyzed coupling reaction strategy has been utilized in the synthesis of two novel BN-perylenes starting from halogenated BN-naphthalene derivatives. The molecular structures and packing modes of BN-perylenes were confirmed by NMR spectroscopy and X-ray single-crystal diffraction experiments. Their photophysical properties were further investigated using UV-vis and fluorescence spectroscopy and DFT calculations. Interestingly, the isosteric BN-insertion in perylene system resulted in stronger π-π stacking interaction both in solid and solution phases. The synthesized BN-perylenes are proved to be highly stable and thus provide a new valuable platform for novel organic materials applications which is otherwise inaccessible to date.

Assessing the Role of BN‐Embedding Position in B2N2‐Perylenes

“…Besides, 2M‐b‐BNNB‐P adopts a clearly hypsochromic absorption maximum (275 nm) compared to NBBN‐P (329 nm) and BNNB‐P (317 nm). This coincides well with the simulated absorption of the molecular fragments (styrene fragment and conjugated alkene fragment) (Figure S16) [23] . 2M‐b‐BNNB‐P also exhibits apparent hypsochromic maximum emission (458 nm) than NBBN‐P (509 nm) and BNNB‐P (488 nm).…”

“…This coincides well with the simulated absorption of the molecular fragments (styrene fragment and conjugated alkene fragment) (Figure S16). [23] 2M-b-BNNB-P also exhibits apparent hypsochromic maximum emission (458 nm) than NBBN-P (509 nm) and BNNB-P (488 nm). Additionally, it exhibits a substantially shorter t (2.61 ns) and larger k r (9:6 � 10 7 s À 1 ) than NBBN-P (17.74 ns, 1:0 � 10 7 s À 1 ) and BNNB-P (9.02 ns, 3:8 � 10 7 s À 1 ) (Figure 5b).…”

“Spine Surgery” of Perylene Diimides with Covalent B–N Bonds toward Electron-Deficient BN-Embedded Polycyclic Aromatic Hydrocarbons

“…According to the time-dependent density functional theory (TD-DFT) calculation (Table S2), this high-energy band can be mainly ascribed to the transitions of HOMO–5 → LUMO+1 and HOMO–6 → LUMO+1, whereas the lowest-energy absorption peak is originated from the HOMO → LUMO excitation with additional involvement of a HOMO–2 → LUMO transition. Very recently, Fang reported another analogue of BN-perylene and explained the origin of this high-energy absorption peak from another standpoint . Due to the less aromatic character of BN-embedded PDIs (Figure f, indicated by the less negative NICS(1)­zz value), the high-energy absorption could originate from the π → π* transition of conjugated alkene segments.…”

Copper-catalyzed nitration of electron-deficient BN-naphthalene

“…The process may be facilitated by p-p stacking attraction of polar ABN rings and optimized by better HOMO-LUMO overlap, which avoids direct IÁ Á ÁI steric interaction and sufficiently lowers the activation barrier for the reaction that converts 3 to 4c. Driven by our persistent interest in late-stage functionalization of ABN systems, [26][27][28][29] we herein report the first synthesis of ABN diiodide 4c (Scheme 1) and the corresponding dihalo-ABN nitro products (5a, 5b and 5c) (Scheme 2). These findings are further substantiated by spectroscopic characterization and X-ray single crystal diffraction experiments.…”